EP3167110A1 - Cable rubberized in situ comprising a rubberizing composition comprising a corrosion inhibitor - Google Patents
Cable rubberized in situ comprising a rubberizing composition comprising a corrosion inhibitorInfo
- Publication number
- EP3167110A1 EP3167110A1 EP15727022.4A EP15727022A EP3167110A1 EP 3167110 A1 EP3167110 A1 EP 3167110A1 EP 15727022 A EP15727022 A EP 15727022A EP 3167110 A1 EP3167110 A1 EP 3167110A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cable
- situ
- gummed
- strand
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 127
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 68
- 238000005260 corrosion Methods 0.000 title description 17
- 230000007797 corrosion Effects 0.000 title description 16
- 239000003112 inhibitor Substances 0.000 title description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 79
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 230000002787 reinforcement Effects 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000002211 L-ascorbic acid Substances 0.000 claims description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 109
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 38
- 230000003014 reinforcing effect Effects 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 17
- 238000004073 vulcanization Methods 0.000 description 15
- 239000011256 inorganic filler Substances 0.000 description 14
- 239000006229 carbon black Substances 0.000 description 13
- 235000019241 carbon black Nutrition 0.000 description 13
- 229910003475 inorganic filler Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 238000005201 scrubbing Methods 0.000 description 11
- 239000003518 caustics Substances 0.000 description 10
- 229920003244 diene elastomer Polymers 0.000 description 10
- 239000012763 reinforcing filler Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 241001441571 Hiodontidae Species 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000010411 cooking Methods 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000016571 aggressive behavior Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 239000012936 vulcanization activator Substances 0.000 description 3
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 206010001488 Aggression Diseases 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000010066 calendering (rubber) Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012345 traction test Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
- D07B1/0606—Reinforcing cords for rubber or plastic articles
- D07B1/0613—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the rope configuration
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
- D07B1/0606—Reinforcing cords for rubber or plastic articles
- D07B1/062—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
- D07B1/0606—Reinforcing cords for rubber or plastic articles
- D07B1/062—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration
- D07B1/0633—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the strand configuration having a multiple-layer configuration
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
- D07B1/165—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber inlay
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
- B60C2009/0021—Coating rubbers for steel cords
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2001—Wires or filaments
- D07B2201/201—Wires or filaments characterised by a coating
- D07B2201/2012—Wires or filaments characterised by a coating comprising polymers
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2015—Strands
- D07B2201/2046—Strands comprising fillers
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2047—Cores
- D07B2201/2052—Cores characterised by their structure
- D07B2201/2059—Cores characterised by their structure comprising wires
- D07B2201/2061—Cores characterised by their structure comprising wires resulting in a twisted structure
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2047—Cores
- D07B2201/2052—Cores characterised by their structure
- D07B2201/2059—Cores characterised by their structure comprising wires
- D07B2201/2062—Cores characterised by their structure comprising wires comprising fillers
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2047—Cores
- D07B2201/2052—Cores characterised by their structure
- D07B2201/2065—Cores characterised by their structure comprising a coating
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2075—Fillers
- D07B2201/2077—Fillers having an anti-corrosive function
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2075—Fillers
- D07B2201/2082—Fillers characterised by the materials used
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2401/00—Aspects related to the problem to be solved or advantage
- D07B2401/20—Aspects related to the problem to be solved or advantage related to ropes or cables
- D07B2401/202—Environmental resistance
- D07B2401/2025—Environmental resistance avoiding corrosion
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2501/00—Application field
- D07B2501/20—Application field related to ropes or cables
- D07B2501/2046—Tire cords
Definitions
- the invention relates to a monotoron cable gummed in situ, a multi-strand cable gummed in situ and the use of such cables for the reinforcement of a semi-finished rubber product and a tire comprising such cables.
- a radial tire comprises in a known manner a tread, two inextensible beads, two flanks connecting the beads to the tread and a belt, or crown reinforcement, disposed circumferentially between the carcass reinforcement and the tread band. rolling.
- the carcass and / or crown reinforcement is constituted in known manner by at least one ply (or "layer") of rubber reinforced by reinforcement elements such as cables, generally of the metal type in the case of tires for industrial vehicles carrying heavy loads.
- monotoron metal cables consist of a core layer or core and one or more layers of concentric son disposed around this core. Cableway three layers most used are essentially cable construction M + N + P, containing a core M fi 'l (s), M ranging from 1 to 4, surrounded by an intermediate layer of N son , N typically ranging from 3 to 12, itself surrounded by an outer layer of P son, P typically ranging from 8 to 20, the assembly may be optionally shrunk by an outer hoop thread wound helically around the layer external. Multistrand metal cables comprising several strands as described above are also used.
- these metal cables are subjected, particularly in the case of the carcass reinforcement, to significant stresses during the rolling of the tires, in particular to repeated bending or variations of curvature inducing at the level of the wires of the tires. friction, particularly as a result of contact between adjacent layers, and therefore wear, as well as fatigue; they must therefore have a high resistance to phenomena known as "fatigue-fretting".
- crown reinforcement a heavy industrial vehicle tire, including civil engineering, is subjected to many attacks. Indeed, the rolling of this type of tire is usually done on a rough surface sometimes leading to perforations of the tread. These perforations allow the entry of corrosive agents, for example air and water, which oxidize the metal reinforcing elements of the crown reinforcement, in particular crown plies, and considerably reduce the service life of the tire. . It is particularly important further that the reinforcing elements are impregnated as much as possible by the rubber, that this material penetrates into all the spaces between the son and / or the strands constituting the cables.
- the application WO 2005/071157 proposed cables with three building layers 1 + M + N, in particular of construction 1 + 6 + 12, one of the essential characteristics is that a sheath made of a rubber composition, called scrubbing, covers at least the intermediate layer consisting of M son, the core (or unit wire) of the cable may itself be covered or not rubber.
- scrubbing a sheath made of a rubber composition
- the cable has excellent fatigue-fretting endurance and resistance to aggression properties that are significantly improved over the cables of the prior art. The longevity of the tires and that of their carcass reinforcement and / or crown are thus very significantly improved.
- JP05177772 discloses a composition comprising a derivative of the family of triazines as a corrosion inhibitor.
- a corrosion inhibitor is relatively expensive.
- the object of the invention is to propose a cable gummed in situ with a rubber scrub composition comprising an effective and environmentally neutral corrosion inhibitor.
- the subject of the invention is a monotoron cable gummed in situ, comprising:
- the rubber composition comprises a compound of formula (I) or (II) or a salt thereof:
- each R1, R2, R3 and R4 independently of one another is -OH, -O-alkyl or -O (C) O-alkyl.
- the compound of formula (I) or (II) or the salt of this compound forms a corrosion inhibitor.
- the rubber scrub composition according to the invention reduces or even eliminate the risk of corrosion of the wire rope.
- the fact of adding a compound of formula (I) or (II) or a salt of this compound in the rubber composition disposed between the inner layer of the cable and the outer layer of the cable makes it possible to reduce the amount of compound while obtaining a similar anticorrosive effect, or better than when said compound is disposed in the adjacent rubber calendering composition.
- the compounds of formula (I) or (II) or the salts of these compounds pick up the corrosive agents before they reach the son protected by the scrubbing composition.
- the composition also makes it possible to limit the corrosive action of the corrosive agents on the yarns. Indeed, it is assumed that the compounds of formula (I) or (II) or the salts of these compounds are transported by the corrosive agent, for example water, to the son where they adsorb on an external surface yarns that the scrubbing composition protects and blocks the action of corrosive agents.
- the compounds of formulas (I) and (II) may be present in the form of one or the other of the possible diastereoisomers.
- the rubber composition can be in raw or vulcanized form.
- the son are coated with a layer of copper or brass which, among other things, improves the adhesion of the rubber to the wire by sulphidation of this layer during cooking.
- the compounds of formula (I) or (II) or the salts of these compounds do not inhibit this sulphidation and therefore do not interfere with adhesion between the metal reinforcing element and the rubber composition.
- the monotoron cable gummed in situ according to the invention may also comprise one or more of the following characteristics, considered individually or in any technically possible combination:
- R1 and R2 represent the -OH group
- R3 and R4 represent the -OH group
- the compound of formula (I) is ascorbic acid and preferably L-ascorbic acid; and or
- the rubber composition comprises at most 2 pce inclusive, preferably at most 1 pce inclusive and more preferably at most 0.7 pce inclusive of the compound of formula (I) or (II) or a salt thereof.
- the rubber composition is present in each of the capillaries located between the one or more N 1 internal thread (s) of the inner layer and the N3 external son of the outer layer.
- the cable further comprises an intermediate layer of the cable comprising N2 intermediate son helically wrapped around the inner layer of the cable, the N3 external son of the outer layer of the cable being helically wound around the middle layer of the cable.
- the rubber composition is present in each of the capillaries located between the N1 or inner thread (s) of the inner layer and N2 intermediate son of the intermediate layer.
- the rubber composition is present in each of the capillaries located between the N2 intermediate son of the intermediate layer and the N3 external son of the outer layer.
- the invention also relates to a multi-strand cable gummed in situ, comprising at least strand being a monotoron cable gummed in situ according to the invention.
- the multi-strand cable gummed in situ comprises:
- an outer layer of the cable comprising T2 outer strands wound helically around the inner layer of the cable
- At least one of the inner and / or outer strands being a monotoron cable gummed in situ according to the invention.
- the multi-strand cable gummed in situ may also include one or more of the following characteristics, considered individually or in any technically feasible combination:
- each outer strand is a monotoron cable gummed in situ according to the invention.
- each inner strand is a monotoron cable gummed in situ according to the invention.
- the multi-strand cable comprises a rubber composition disposed between the inner layer of the inner strand (s) of the cable and the outer layer of the outer two strands of the cable, the rubber composition comprising a compound formula (I) or (II) or a salt of this compound:
- the invention also relates to a multi-strand cable gummed in situ, comprising:
- an outer layer of the cable comprising T2 outer strands wound helically around the inner layer of the cable
- the rubber composition comprising a compound of formula (I) or (II) or a salt thereof:
- each R1, R2, R3 and R4 independently of one another is -OH, -O-alkyl or -O (C) O-alkyl.
- the invention also relates to the use of a monotoron cable gummed in situ according to the invention or a multi-strand cable gummed in situ according to the invention for the reinforcement of an article or semi-finished product rubber, for example a tire.
- the invention further relates to a tire comprising a monotoron cable gummed in situ according to the invention or to a multi-strand cable gummed in situ according to the invention.
- FIG. 1 is a diagrammatic representation of a cross-section of a monotoron cable of construction 1 + 6, gummed in situ, according to the invention
- FIGS. 2 to 4 are diagrammatic representations of cross-sections of monotoron cables of construction 1 + 6 + 12, gummed in situ, according to various embodiments of the invention.
- FIGS. 5 to 10 are diagrammatic representations of cross-sections of multi-strand cables of construction 1 + 6, gummed in situ, and according to various embodiments of the invention and comprising several strands of structure 1 + 6 + 12. [035] In the present description, unless otherwise expressly indicated, all the percentages (%) indicated are% by weight. The acronym “pce” means parts by weight per hundred parts of elastomer.
- each capillary comprises at least one rubber stopper.
- the invention relates to a monotoron cable gummed in situ C comprising at least one inner layer of the cable CT1 and an outer layer of the cable CT3.
- the inner layer of the cable CT1 comprises N1 internal wire (s) with N1 greater than or equal to 1.
- the outer layer of the cable CT3 comprises N3 external wires wound helically around the inner layer of the cable CT1.
- the inner layer CT1 may comprise one or more son (i.e. N1 ranges from 1 to 3).
- the outer layer CT3 may comprise from ten to fourteen threads (i.e., N3 ranges from 5 to 7).
- the cable according to the invention is erased in situ and therefore comprises a so-called scrub rubber composition disposed between the inner layer of the cable CT1 and the outer layer of the cable CT3.
- the rubber (or indistinctly "elastomer”, both being considered synonymous) of the scrub composition 20 is preferably a diene elastomer, that is to say by definition an elastomer derived at least in part (that is to say a homopolymer or a copolymer) of monomer (s) diene (s) (ie, monomer (s) carrier (s) of two carbon-carbon double bonds, conjugated or not).
- the diene elastomer of the composition is chosen from the group of diene elastomers consisting of polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers , isoprene copolymers and mixtures of these elastomers.
- Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), copolymers of isoprene-butadiene-styrene (SBIR) and mixtures of such copolymers.
- SBR butadiene-styrene copolymers
- BIR isoprene-butadiene copolymers
- SIR isoprene-styrene copolymers
- SBIR copolymers of isoprene-butadiene-styrene
- compositions may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, by example of thermoplastic polymers.
- the composition comprises a reinforcing filler.
- a reinforcing filler When a reinforcing filler is used, it is possible to use any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for the manufacture of tires, for example an organic filler such as carbon black, a filler reinforcing inorganic such as silica, or a blend of these two types of filler, including a blend of carbon black and silica.
- an organic filler such as carbon black
- a filler reinforcing inorganic such as silica
- a blend of these two types of filler including a blend of carbon black and silica.
- Suitable carbon blacks are all carbon blacks conventionally used in tires (so-called pneumatic grade blacks). For example, mention will be made more particularly of reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades).
- any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called “white” charge, charge “clear” or “non-black filler” as opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition for manufacturing In other words, it is capable of replacing, in its reinforcing function, a conventional carbon black of pneumatic grade, which load is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) at its stage. area.
- -OH hydroxyl groups
- reinforcing inorganic filler is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
- reinforcing inorganic filler also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
- Suitable inorganic reinforcing fillers are, in particular, mineral fillers of the siliceous type, in particular silica (SiO 2), or of the type aluminous material, in particular alumina (Al 2 O 3).
- the silica used may be any reinforcing silica known to those skilled in the art, especially any precipitated or pyrogenated silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / boy Wut.
- HDS highly dispersible precipitated silicas
- an at least bifunctional coupling agent (or bonding agent) is used in known manner in order to ensure a sufficient chemical and / or physical connection between the inorganic filler (surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
- the total reinforcing filler content (carbon black and / or reinforcing inorganic filler such as silica) is within a range from 5 to 120 phr inclusive, more preferably 5 to 70 phr inclusive and more preferably also 5 to 60 pce terminals included.
- an inorganic filler for example silica
- its level is within a range from 0 to 70 phr included terminals, preferably from 0 to 60 pce included terminals, in particular also from 5 to 70 pce inclusive terminals, and even more preferably this proportion varies from 5 to 60 pce inclusive terminals.
- the scrub composition 20 comprises a reinforcing filler comprising predominantly by weight of the silica and more preferably comprising only silica. For the most part, it is understood that the proportion by weight of silica is greater than the proportion by weight of the rest of the other reinforcing fillers of the composition, whether these fillers are organic, for example carbon black, or inorganic.
- the scrubbing composition 20 comprises at least 30 pce inclusive and preferably at least 40 pce included silica terminal.
- the scrub composition 20 comprises various additives.
- the scrubbing compositions may also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, for example plasticizers or extension oils, which are of an aromatic nature. or non-aromatic, pigments, protective agents such as anti-oxidants, anti-fatigue agents, reinforcing resins such as bismaleimides, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M).
- plasticizers or extension oils which are of an aromatic nature. or non-aromatic, pigments, protective agents such as anti-oxidants, anti-fatigue agents, reinforcing resins such as bismaleimides, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M).
- the scrubbing composition comprises a corrosion inhibitor according to formulas (I) or (II) or salts thereof:
- each R1, R2, R3 and R4 independently of one another is -OH, -O-alkyl or -O (C) O-alkyl.
- R1 and R2 are identical.
- R1 and R2 are identical they are preferably an -OH group.
- R3 and R4 are identical.
- R1 and R2 are the same, they are preferably an -OH group.
- the compound of formula (I) is ascorbic acid and preferably more preferably L-ascorbic acid.
- the scrub rubber composition 20 comprises at most 2 pce inclusive, preferably at most 1 pce inclusive and more preferably at most 0.7 pce inclusive of the compound of formula (I) or (inclusive). II) or a salt of this compound.
- the scrubbing composition 20 comprises a crosslinking system, more preferably a vulcanization system.
- the crosslinking system here vulcanization comprises sulfur-donor agents, for example sulfur.
- the vulcanization system comprises vulcanization activators such as zinc oxide and stearic acid.
- the vulcanization system comprises an accelerator.
- the accelerator is chosen from tetrabenzylthiuram disulfide (abbreviated "TBZTD”) and the sulfenamide family consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated as “CBS”), N, N-dicyclohexyl-2-benzothiazyl sulfenamide (abbreviated “DCBS”), N-tert-butyl-2-benzothiazyl sulfenamide (abbreviated as "TBBS”), tert-butyl-2-benzothiazylsulfenimide (abbreviated "TBSI”) and mixtures of these compounds.
- MBTS 2-mercaptobenzothiazyl disulfide
- CBS N-cyclohexyl-2-benzothiazyl sulfenamide
- DCBS N
- the vulcanization system also comprises a vulcanization retarder such as N- (cyclohexylthio) phthalimide (abbreviated "CTP").
- a vulcanization retarder such as N- (cyclohexylthio) phthalimide (abbreviated "CTP").
- the sulfur or sulfur donor agent is used at a preferential rate of between 0.5 and 10 pce inclusive limits, more preferably between 0.5 and 8.0 pce inclusive limits and very preferably between 2.0 and 8. , 0 pce terminals included. All accelerators, retarders and vulcanization activators are used at a preferential rate of between 0.5 and 15 pce inclusive. The vulcanization activator (s) is or are used at a preferential rate of between 0.5 and 10 pb inclusive.
- composition free of a compound it is understood that the composition does not include this compound voluntarily introduced into the composition and that this compound, if present, is in the form of traces related for example to the process of manufacture of the composition.
- the composition lacking a compound comprises the latter in an amount less than or equal to 0.1 phr and preferably less than or equal to 0.05 phr.
- the inner layer CT1 of the monotoron cable gummed in situ C comprises an inner wire 10 and the outer layer of the cable CT3 comprising six outer wires 13 wound helically around the inner wire.
- the scrub rubber composition 20 is present in each of the capillaries or interstices located between the inner wire of the inner layer CT1 and the six outer wires of the outer layer CT3.
- monotoron cable gummed in situ according to the invention C may comprise an intermediate layer of the cable CT2 comprising N2 intermediate son.
- the N2 intermediate son are helically wound around the inner layer CT1 of the cable and the N3 external son of the outer layer CT3 of the cable are helically wound around the intermediate layer CT2 of the cable.
- the inner layer CT1 comprises an inner wire 10
- the intermediate layer CT2 comprises six intermediate son 12
- the outer layer CT3 comprises twelve outer son 13.
- the cables of Figures 2 at 4 have a structure 1 + 6 + 12.
- the inner layer CT1 may comprise more son, for example two or three son assembled together (i.e. N 1 varies from 1 to 3).
- the intermediate layer CT2 may comprise five to seven wires (i.e. N2 ranges from 5 to 7).
- the outer layer CT3 may comprise from ten to fourteen threads (i.e., N3 ranges from 10 to 14).
- the scrub rubber composition 20 is present in each of the capillaries located between the inner wire 10 of the inner layer CT1 and the six intermediate wires 12 of the intermediate layer CT2.
- the rubber degumming composition 20 is present in each of the capillaries situated between the six intermediate wires 12 of the intermediate layer CT2 and the twelve outer wires 13 of the outer layer CT3.
- Such a configuration makes it possible to provide good protection against corrosion of the intermediate and external wires.
- the scrub composition 20 thus makes it possible to form an anticorrosive protection barrier between the core of the cable and the outside.
- the scrub composition 20 is present in each of the capillaries located between the inner wire 10 of the inner layer CT1 and the six intermediate wires 12 of the intermediate layer CT2 and in each of the capillaries located between the six intermediate wires 12 of the intermediate layer CT2 and the twelve external wires 13 of the outer layer CT3.
- the invention also relates to a multi-strand cable gummed in situ C comprising at least one inner layer of the cable CCI and an outer layer of the cable CCE cable.
- the inner layer of the CCI cable comprises T1 internal strand (s).
- the outer layer of the CCE cable comprises T2 outer strands wound helically around the inner layer CCI of the C cable.
- Each internal strand T1 and external TE is a single-strand cable comprising at least an inner layer of the cable CT1 and an outer layer of the cable CT3.
- the inner layer comprises N1 internal thread (s) and the outer layer comprises N3 outer threads helically wrapped around the inner layer of the cable.
- each inner strand T1 and external TE is a monotoron cable comprises an intermediate layer CT2.
- the intermediate layer of the cable CT2 comprises N2 intermediate wires wound helically around the inner layer CT1 of the cable, the outer N3 son of the outer layer CT3 of the cable being helically wound around the intermediate layer CT2 of the cable.
- the multi-strand cables C according to the invention are not limited to cables comprising strands of structures shown in FIGS. 5 to 10.
- At least one of the inner and / or outer strands is a monotoron cable according to the invention, namely a monotoron cable gummed in with a rubber composition comprising a compound of
- each R1, R2, R3 and R4 independently of one another is -OH, -O-alkyl or -O (C) O-alkyl.
- each outer strand TE is a monotoron cable gummed in situ according to the invention as described with reference to FIG. 4.
- each inner strand T1 is a monotoron cable gummed in situ according to the invention as described with reference to FIG. 4.
- each outer strand TE and each inner strand T1 is a monotoron cable gummed in situ according to the invention as described with reference to FIG. 4.
- the multi-strand cables according to the invention may comprise a scrub rubber composition 20 disposed between the inner layer CCI of the inner strand T1 of the cable and the outer layer CCE outer strands TE of the cable, the scrub rubber composition comprising a compound of formula (I) or (II) or a salt thereof
- each R1, R2, R3 and R4 independently of one another is -OH, -O-alkyl or -O (C) O-alkyl.
- the rubber scrub composition 20 is the same as that described above for the cables shown.
- each outer strand TE is a monotoron cable gummed in situ according to the invention as described with reference to FIG. 4, the inner strand is a non-gummed strand in situ and a gummy rubber composition comprising a compound of formula (I) or (II) wherein the salts of these compounds are disposed between the inner layer of the CCI cable and the outer layer of the CCE cable.
- the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for the single-rod cables.
- each outer strand TE and each inner strand T1 is a monotoron cable gummed in situ according to the invention and a scrub rubber composition comprising a compound of formula (I) or (II) or the salts of these compounds is disposed between the inner layer of the CCI cable and the outer layer of the CEC cable.
- the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for the single-rod cables.
- the invention also relates to a multi-strand cable gummed in situ C comprising at least:
- an outer layer CCE of the cable comprising T2 outer strands TE wound helically around the inner layer CCI of the cable
- a rubber composition disposed between the inner layer CCI of the cable and the outer layer CCE of the cable, the rubber composition comprising a compound of formula I) or (II) or a salt of this compound:
- each R1, R2, R3 and R4 independently of one another is -OH, -O-alkyl or -O (C) O-alkyl.
- the strands are monotoron cables not gummed in situ.
- a scrub rubber composition comprising a compound of formula (I) or (II) or salts thereof is disposed between the inner layer of the CCI cable and the outer layer of the ECC cable.
- the scrub rubber composition 20 disposed between the inner layer of the CCI cable and the outer layer of the CCE cable is the same as previously described for single-rod cables.
- the invention also relates to the use of a cable according to the invention for reinforcing articles or semi-finished products made of plastic and / or rubber, for example plies, pipes, belts, conveyor belts, tires, more particularly tires for industrial vehicles.
- the rubber scrub composition 20 is available in accordance with the general knowledge of those skilled in the art during the assembly of the different layers of the cable. Reference is especially made to publications EP1699973, WO2006 / 013077, WO2007 / 090603, WO09 / 083212, WO09 / 083213, WO10 / 012411, WO10 / 054790, WO10 / 054791, WO10 / 112444, WO10 / 112445, WO10 / 139583, WO11 / 000963, WO11 / 000964, WO11 / 000950 and WO11 / 000951.
- the cable of the invention is particularly intended to be used as a reinforcing element for industrial vehicles chosen from light trucks, "heavy vehicles” - ie, subway, bus, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles, agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
- industrial vehicles chosen from light trucks, "heavy vehicles” - ie, subway, bus, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles, agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
- the cable according to the invention can be used to reinforce different parts of the tires, in particular carcass reinforcement, crown reinforcement of such tires, in particular of industrial tires such as heavy goods vehicles or civil engineering.
- the invention also relates to these articles or semi-finished products made of plastic and / or rubber themselves when reinforced by a cable according to the invention, in particular the tires intended for the industrial vehicles mentioned. above, more particularly heavy-duty tires or civil engineering, as well as composite fabrics comprising a matrix of rubber composition of rubber reinforced with a gummed cable in situ according to the invention, usable as carcass reinforcement ply or top of such tires.
- COMPARATIVE TESTS COMPARATIVE TESTS
- the corrosion inhibitor of the "Invention” composition is in accordance with formula (I). This is in this case L-ascorbic acid of formula (III) below.
- the "Invention" composition comprises at most 2 pce inclusive, preferably at most 1 pce inclusive and more preferably at most 0.7 pce included terminal of the compound of formula (III).
- the diene elastomer is natural rubber.
- the silica is a silica type "HD” - "Zeosil 1 165MP" of the company RHODIA.
- the carbon black is of the N330 type.
- the antioxidant is N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine ("Santoflex 6-PPD” from the company FLEXSYS).
- the organosilane is TESPT ("Si69" from DEGUSSA).
- the cobalt salt is cobalt naphthenate.
- the vulcanization accelerator is N-cyclohexyl-2-benzothiazyl sulfenamide (“Santocure CBS” from FLEXSYS).
- the vulcanization retarder of the composition T is N- (cyclohexylthio) phthalimide (CAS No. 17796-82-6).
- compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes called “non-productive” phase) to high temperature, up to a maximum temperature (denoted Tmax) between 1 10 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (sometimes called phase " productive ") at a lower temperature, typically below 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system or vulcanization; such phases have been described for example in the aforementioned documents EP 501227, EP 735088, WO00 / 05300, WO00 / 05301 or W002 / 083782.
- the first (non-productive) phase is carried out in a single thermomechanical step during which, in a suitable mixer such as a conventional internal mixer, all the constituents are initially introduced.
- a suitable mixer such as a conventional internal mixer
- the necessary basic materials die elastomer, reinforcing inorganic filler and coupling agent
- the second step for example after one to two minutes of mixing, any additional processing agents and other various additives, with the exception of vulcanization system.
- the apparent density of the reinforcing inorganic filler is low (general case of silicas), it may be advantageous to split its introduction into two or more parts.
- thermomechanical work can be added in this internal mixer, after falling of the mixture and cooling intermediate (cooling temperature preferably below 100 ° C), in order to subject the compositions a complementary thermomechanical treatment, in particular to further improve the dispersion in the elastomeric matrix of the reinforcing inorganic filler and its coupling agent .
- the total mixing time, in this non-productive phase, is preferably between 2 and 10 minutes.
- the vulcanization system After cooling the mixture thus obtained, then incorporating, if necessary, the vulcanization system at low temperature, generally in an external mixer such as a roller mixer; the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 minutes.
- the final composition thus obtained is then calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile.
- the vulcanization (or cooking) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, preferably under pressure, for a sufficient time which may vary for example between 5 and 90 min in particular the baking temperature, the vulcanization system adopted, the vulcanization kinetics of the composition in question or the size of the tire.
- a tearout test is carried out according to ASTM D2229 on test specimens comprising metal cables 2.30NF structure of which a portion is interposed between two strips made in the prepared rubber composition and another portion is left free.
- the force required to pull the cable from the two rubber bands is measured. The measurement is made for 15 cables. The value used is the average of the measurements on these 15 cables. The higher the value of the force, the greater the adhesion between the cable and the rubber composition.
- the force required for tearing is greater than the force required to tear the cables of the test specimen, the adhesion of the cables to the tested rubber composition is better than the of the control sample and therefore the relative value retained is greater than 100 (the relative value of the test sample is equal to 100). Conversely, if, for a given composition, the force required for tearing is less than the force required to tear the cables of the test piece, the adhesion of the cables to the rubber composition tested is less good than that of the test specimen and therefore the relative value retained is less than 100.
- the adhesion test described above is carried out with specimens cured and / or aged under different conditions A, B, C, D, E and F.
- condition A normal cooking corresponds to a test performed on a test piece cooked for less than 1 hour at a temperature above 100 ° C.
- Condition B (overcooking) corresponds to a test performed on a specimen fired for a period greater than 1 hour at a temperature above 100 ° C.
- Condition C (wet wet aging) corresponds to a test carried out on a specimen comprising the raw composition and aged for several days at a temperature above 30 ° C and at more than 50% relative humidity.
- condition D (aging in a corrosive atmosphere) corresponds to a test carried out on a specimen comprising the raw composition and aged for several days in an NaCl solution.
- Condition E vapor aging corresponds to a test carried out on a specimen comprising the raw composition and aged for several hours at a temperature above 100 ° C.
- Condition F cooked wet aging corresponds to a test carried out on a specimen fired for a period of less than 1 hour at a temperature above 100 ° C. and aged for several days at a temperature above 30 ° C. and at more than 50% relative humidity.
- composition "Invention” has adhesion performance at least equivalent to the composition T of the state of the art whatever the test conditions except in conditions D (aging in a corrosive atmosphere) and F (wet aging). baked), conditions for which the composition “Invention” has adhesion properties higher than those of the composition T of the state of the art.
- the composition "Invention” thus makes it possible to inhibit the corrosion created by the corrosive agents of conditions D and F. ⁇ 0135 ⁇ Properties before cooking
- the stresses at break (in MPa) and elongations at break (in%) are measured at 23 ° C. ⁇ 2 ° C., and under normal humidity conditions (50 ⁇ 5% relative humidity). ).
- some son could be of non-circular section, for example plastically deformed, in particular with a substantially oval or polygonal section, for example triangular, square or rectangular.
- the son of circular section or not, for example a corrugated wire, may be twisted, twisted helical or zig-zag.
- the diameter of the wire represents the diameter of the cylinder of imaginary revolution which surrounds the wire (space diameter), and no longer the diameter (or any other transverse size, if its section is not circular) of the core wire itself.
- linear son that is to say right, and conventional circular cross section.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1455344A FR3022262B1 (en) | 2014-06-12 | 2014-06-12 | IN SITU GUM CABLE COMPRISING A SCRUB COMPOSITION COMPRISING A CORROSION INHIBITOR |
PCT/EP2015/063019 WO2015189314A1 (en) | 2014-06-12 | 2015-06-11 | Cable rubberized in situ comprising a rubberizing composition comprising a corrosion inhibitor |
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EP3167110A1 true EP3167110A1 (en) | 2017-05-17 |
EP3167110B1 EP3167110B1 (en) | 2018-06-06 |
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EP15727022.4A Active EP3167110B1 (en) | 2014-06-12 | 2015-06-11 | Cable rubberized in situ comprising a rubberizing composition comprising a corrosion inhibitor |
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US (1) | US20180155526A1 (en) |
EP (1) | EP3167110B1 (en) |
JP (1) | JP6293312B2 (en) |
CN (1) | CN106661828B (en) |
FR (1) | FR3022262B1 (en) |
WO (1) | WO2015189314A1 (en) |
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FR3104591A1 (en) | 2019-12-16 | 2021-06-18 | Compagnie Generale Des Etablissements Michelin | Reinforced product based on at least one metallic reinforcing element and a rubber composition. |
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US20200308367A1 (en) * | 2017-10-31 | 2020-10-01 | Bridgestone Corporation | Rubber composition, metal-rubber composite, and tire |
CN109281211A (en) * | 2018-08-01 | 2019-01-29 | 江苏杰力钢缆索具有限公司 | A kind of high stability wirerope and preparation method thereof |
CN113583306A (en) * | 2021-08-19 | 2021-11-02 | 江西立德汽车零部件有限公司 | High-strength anti-corrosion rubber sheath |
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JPH06272067A (en) * | 1993-03-19 | 1994-09-27 | Yoko Inoue | Rust preventing method |
FR2732351B1 (en) | 1995-03-29 | 1998-08-21 | Michelin & Cie | RUBBER COMPOSITION FOR A TIRE ENCLOSURE CONTAINING ALUMINUM DOPED SILICA AS A REINFORCING FILLER |
US5859101A (en) * | 1996-03-04 | 1999-01-12 | The Yokohama Rubber Co. Ltd. | Rubber composition for tire |
JPH10158435A (en) * | 1996-12-02 | 1998-06-16 | Yokohama Rubber Co Ltd:The | Tire rubber composition |
JP3735432B2 (en) * | 1996-03-04 | 2006-01-18 | 横浜ゴム株式会社 | Rubber composition for tire |
JPH10279735A (en) * | 1997-04-07 | 1998-10-20 | Bridgestone Corp | Rubber composition and pneumatic tire using oxygen absorbent |
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JP2005307368A (en) * | 2004-04-19 | 2005-11-04 | Yokohama Rubber Co Ltd:The | Steel cord and pneumatic radial tire using the same |
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FR2925923B1 (en) | 2007-12-28 | 2009-12-18 | Michelin Soc Tech | METHOD AND DEVICE FOR MANUFACTURING A TWO-LAYER CABLE OF THE TYPE IN SITU GUM |
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FR2934614B1 (en) | 2008-08-01 | 2010-09-10 | Michelin Soc Tech | IN SITU GAS BED CABLE FOR PNEUMATIC CARCASE REINFORCEMENT. |
FR2938557B1 (en) | 2008-11-17 | 2011-02-18 | Michelin Soc Tech | THREE-LAYER CABLE, IN SITU GUM, FOR PNEUMATIC CARCASS REINFORCEMENT |
FR2938558B1 (en) | 2008-11-17 | 2010-12-31 | Michelin Soc Tech | METHOD AND DEVICE FOR MANUFACTURING A THREE LAYER CABLE OF THE TYPE IN SITU GUM. |
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FR2947577B1 (en) | 2009-07-03 | 2013-02-22 | Michelin Soc Tech | METAL CABLE WITH THREE LAYERS GUM IN SITU CONSTRUCTION 3 + M + N |
FR2947576B1 (en) | 2009-07-03 | 2011-08-19 | Michelin Soc Tech | METAL CABLE WITH THREE LAYERS GUM IN SITU CONSTRUCTION 2 + M + N |
FR2947575B1 (en) | 2009-07-03 | 2011-08-19 | Michelin Soc Tech | CABLE MULTITORONS WHOSE ELEMENTARY TORONES ARE CABLES WITH TWO LAYERS GOMMES IN SITU. |
EA201290089A1 (en) * | 2009-09-04 | 2012-09-28 | ГЛАКСОСМИТКЛАЙН ЭлЭлСи | CHEMICAL COMPOUNDS |
FR2962453B1 (en) * | 2010-05-20 | 2012-09-21 | Michelin Soc Tech | THREE-LAYER METAL CABLE, GUM IN SITU BY UNSATURATED THERMOPLASTIC ELASTOMER |
JP5485841B2 (en) * | 2010-09-15 | 2014-05-07 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
JP5948118B2 (en) * | 2012-04-16 | 2016-07-06 | 株式会社ブリヂストン | Method for producing natural rubber, method for producing rubber composition containing natural rubber, and method for producing tire |
JP2014162894A (en) * | 2013-02-27 | 2014-09-08 | Bridgestone Corp | Rubber composition, method of producing rubber-metal composite, rubber-metal composite, tire, industrial belt and rubber roller |
-
2014
- 2014-06-12 FR FR1455344A patent/FR3022262B1/en not_active Expired - Fee Related
-
2015
- 2015-06-11 US US15/317,715 patent/US20180155526A1/en not_active Abandoned
- 2015-06-11 CN CN201580039058.XA patent/CN106661828B/en not_active Expired - Fee Related
- 2015-06-11 EP EP15727022.4A patent/EP3167110B1/en active Active
- 2015-06-11 WO PCT/EP2015/063019 patent/WO2015189314A1/en active Application Filing
- 2015-06-11 JP JP2016572638A patent/JP6293312B2/en active Active
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3104591A1 (en) | 2019-12-16 | 2021-06-18 | Compagnie Generale Des Etablissements Michelin | Reinforced product based on at least one metallic reinforcing element and a rubber composition. |
WO2021123587A1 (en) | 2019-12-16 | 2021-06-24 | Compagnie Generale Des Etablissements Michelin | Hardened product comprising at least one metal hardening element and a rubber composition |
Also Published As
Publication number | Publication date |
---|---|
CN106661828A (en) | 2017-05-10 |
JP6293312B2 (en) | 2018-03-14 |
FR3022262A1 (en) | 2015-12-18 |
JP2017521567A (en) | 2017-08-03 |
US20180155526A1 (en) | 2018-06-07 |
WO2015189314A1 (en) | 2015-12-17 |
FR3022262B1 (en) | 2016-06-03 |
EP3167110B1 (en) | 2018-06-06 |
CN106661828B (en) | 2019-01-15 |
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